EP0340070B1 - Process for the synthesis of iron (iii) chloride - Google Patents

Process for the synthesis of iron (iii) chloride Download PDF

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Publication number
EP0340070B1
EP0340070B1 EP19890401038 EP89401038A EP0340070B1 EP 0340070 B1 EP0340070 B1 EP 0340070B1 EP 19890401038 EP19890401038 EP 19890401038 EP 89401038 A EP89401038 A EP 89401038A EP 0340070 B1 EP0340070 B1 EP 0340070B1
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Prior art keywords
reactor
chloride
ferric chloride
chlorine
ferrous
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EP19890401038
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German (de)
French (fr)
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EP0340070A1 (en
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René Clair
Alain Gallet
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Arkema France SA
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Elf Atochem SA
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00—Compounds of iron
    • C01G49/10—Halides
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S423/00—Chemistry of inorganic compounds
    • Y10S423/01—Waste acid containing iron

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  • the present invention relates to a process for the synthesis of ferric chloride and more particularly to the chlorination of ferrous chloride in aqueous solution.
  • This ferric chloride is used as a flocculating agent in water treatment.
  • the simplest method is to attack iron with concentrated hydrochloric acid, thus obtaining a solution of about 36% by weight of ferrous chloride (FeCl2) which is chlorinated to obtain a solution of ferric chloride (FeCl3) titrating about 41% by weight and directly usable as a flocculating agent.
  • This 41% solution is the usual commercial form.
  • US-A-4,066,748 describes a process starting from a solution of FeCl2 coming from a pickling bath. This process forces ferrous chloride to be concentrated and requires chlorination in two stages.
  • This patent shows in example 3 the impossibility using a single reactor to completely chlorinate ferrous chloride with the stoichiometric amount of chlorine, or the obligation to use an excess of chlorine to chlorinate all ferrous chloride.
  • the present invention relates to a process for the synthesis of ferric chloride from ferrous chloride and in the presence of ferric chloride, characterized in that it consists in introducing the major part of the ferrous chloride at the top of a reactor essentially vertical, to introduce the major part of the chlorine at the bottom of the reactor, to introduce a lateral stream of ferric chloride into the reactor and to collect at the bottom of said reactor a solution containing essentially ferric chloride.
  • the reactor ensures contact between chlorine and ferrous and ferric chloride.
  • the reactor is essentially vertical, that is to say that it is a capacity such that the smallest cylinder which contains this capacity has a generator at least equal to the diameter of its circular section, this generator being vertical or close to the vertical.
  • a column of the distillation column or absorption column type is used.
  • a column is used fitted with gas / liquid contact devices such as trays or ring linings or more than one of these devices.
  • the height of this column can be between 0.1 and 40 meters, and preferably between 2 and 20 meters.
  • Ferrous chloride is in the form of an aqueous solution, as is ferric chloride. Most of the ferrous chloride, i.e. at least half of the solution, is introduced to the top of the reactor, and the remainder of the ferrous chloride solution can be introduced at different heights provided, however, that it is above the chlorine supply which is closest to the bottom of the reactor, that is to say which geometrically is the lowest.
  • the ferrous chloride is introduced in a single stream at the top of the reactor.
  • Ferrous chloride is in the form of an aqueous solution essentially containing ferrous chloride but which may already contain ferric chloride and / or hydrochloric acid.
  • Liquid or gaseous chlorine or a gas or a liquid containing chlorine can be used .
  • chlorine is introduced at the bottom of the reactor.
  • the inert materials contained in the chlorine and possibly unreacted chlorine are collected at the top of the reactor in the gas phase.
  • the reactor is supplied with a side stream of ferric chloride, this stream is in the form of an aqueous solution essentially containing ferric chloride.
  • lateral means that we introduce ferric chloride between the supply of ferrous chloride at the top and the supply of chlorine at the foot. It would not be departing from the scope of the invention to use a solution containing up to 1% by weight of ferrous chloride.
  • This ferric chloride can also contain a little HCl.
  • Ferric chloride can be introduced laterally at several points. Advantageously, it is introduced all at once and preferably in the upper third of the reactor.
  • a ferrous chloride solution and a ferric chloride solution containing not more than 1% by weight of HCl expressed relative to the weight of the two ferrous and ferric chloride solutions are used, which allows ferric chloride to be used directly as flocculating agent for water treatment.
  • the reactor operates at a moderate temperature, that is to say such that this temperature added to the residence time does not cause hydrolysis of the FeCl2.
  • a residence time of the ferrous chloride is respected of at least 10 seconds in the reactor, and preferably less than 4 hours.
  • ferric chloride It is not necessary to chlorinate all the FeCl2, the specifications of ferric chloride can sometimes tolerate 0.1 to 1% by weight of FeCl2 in the ferric chloride solution. It would not be departing from the scope of the invention to use an excess of chlorine relative to the stoichiometry.
  • the temperature of the reaction medium is between 50 and 100 ° C.
  • the pressure can be arbitrary, for convenience, it operates between atmospheric pressure and 6 bars, and preferably between atmospheric pressure and 1 bar relative.
  • a solution containing essentially ferric chloride is collected at the bottom of the reactor. According to a preferred form of the invention, this solution is recycled to the reactor as a lateral supply of ferric chloride.
  • a quantity of ferric chloride corresponding to the quantity of ferrous chloride introduced into the reactor is withdrawn before recycling.
  • This racking constitutes the production of ferric chloride.
  • the ferric chloride solution can optionally be reheated before evaporation.
  • FIG. 1 represents an example of implementation of the invention.
  • the column (1) which comprises two packing beds (7) and (8) is supplied with (2) ferrous chloride, (3) chlorine and (4) ferric chloride.
  • the inert materials contained in the chlorine stream (3) are collected in (6) and in a ferric chloride solution (5).
  • FIG. 2 represents another implementation of the invention. (The same number is used as in Figure 1).
  • the ferric chloride solution (5) is expanded in (12).
  • the liquid phase (11) is divided into a stream (9) which constitutes the production of ferric chloride and a stream (4) which is recycled to the reactor (1).
  • the expansion pot (12) is connected by (10) to a steam ejector. (13) is a heat exchanger.
  • a device is used in accordance with FIG. 2 in which the column (1) is made of glass with an internal diameter of 0.35 m and has a packing height of 7 m for the part (7) and 3 m for the part (8) .
  • a solution of 296 kg / h of FeCl2 and 704 kg / h of water at 80 ° C. is introduced in (2) and in (3) a flow rate of 82.7 kg / h of chlorine and 5 kg / h of inert.
  • the 5 kg / h inert material is collected in (6) and in (5) a solution of ferric chloride at 85 ° C.
  • Column (1) operates at a pressure of 1.1 bar absolute.
  • the ferric chloride is heated from 85 to 94 ° C by the exchanger (13), then it is expanded to a pressure of 0.25 bar absolute.
  • a solution containing 2272 kg / h of FeCl3 and 3269 kg / h of water is recycled in (4) and it is drawn off in (10) 379 kg / h of FeCl3 diluted in 545 kg / h of water.
  • Example 1 The procedure is as in Example 1 but by feeding the column (1) with ferrous chloride between the two beds (7) and (8), that is to say at the same height as the recycling (4). To obtain the same conversion of FeCl2 to FeCl3 it was necessary to increase the chlorine flow rate to 88 kg / h, that is to say 88 kg / h of chlorine and 5.32 kg / h of inert materials. The excess of chlorine and the inert materials come out in (6).

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Respiratory Apparatuses And Protective Means (AREA)
  • Compounds Of Iron (AREA)

Abstract

Process for the synthesis of ferric chloride consisting in introducing ferrous chloride at the top of a vertical reactor, introducing chlorine at the bottom of the reactor and introducing a side stream of ferric chloride. <??>This process allows all the ferrous chloride to be converted by employing the stoichiometric quantity of chlorine.

Description

La présente invention concerne un procédé de synthèse du chlorure ferrique et plus particulièrement la chloration du chlorure ferreux en solution aqueuse. Ce chlorure ferrique est utilisé comme agent floculant dans le traitement des eaux. On peut se reporter au KIRK OTHMER 3ème édition, volume 24, pages 394-396 (1984) et au volume 10, page 498 (1980) où figure cette application. Le procédé le plus simple consiste à attaquer du fer par de l'acide chlorhydrique concentré, on obtient ainsi une solution à environ 36% en poids de chlorure ferreux (FeCl₂) qu'on chlore pour obtenir une solution de chlorure ferrique (FeCl₃) titrant environ 41% en poids et directement utilisable comme agent floculant. Cette solution à 41% est la forme commerciale habituelle. Il est nécessaire d'obtenir une solution concentrée de FeCl₂ puisque le FeCl₂ et le FeCl₃ peuvent lors d'une concentration par évaporation subir une hydrolyse partielle donnant HCl. La présence d'HCl dans le FeCl₃ est gênante pour le traitement des eaux. Ce procédé nécessite l'utilisation d'acide chlorhydrique concentré.The present invention relates to a process for the synthesis of ferric chloride and more particularly to the chlorination of ferrous chloride in aqueous solution. This ferric chloride is used as a flocculating agent in water treatment. We can refer to the KIRK OTHMER 3rd edition, volume 24, pages 394-396 (1984) and to volume 10, page 498 (1980) where this application appears. The simplest method is to attack iron with concentrated hydrochloric acid, thus obtaining a solution of about 36% by weight of ferrous chloride (FeCl₂) which is chlorinated to obtain a solution of ferric chloride (FeCl₃) titrating about 41% by weight and directly usable as a flocculating agent. This 41% solution is the usual commercial form. It is necessary to obtain a concentrated solution of FeCl₂ since FeCl₂ and FeCl₃ can during a concentration by evaporation undergo a partial hydrolysis giving HCl. The presence of HCl in FeCl₃ is a nuisance for water treatment. This process requires the use of concentrated hydrochloric acid.

Le brevet US-A-3.682.592 décrit un procédé dans lequel la solution de chlorure ferreux est mise en contact avec de l'oxygène.US-A-3,682,592 describes a process in which the ferrous chloride solution is contacted with oxygen.

Le brevet US-A-4.066.748 décrit un procédé à partir d'une solution de FeCl₂ venant d'un bain de décapage. Ce procédé oblige à concentrer le chlorure ferreux et nécessite une chloration en deux étapes.US-A-4,066,748 describes a process starting from a solution of FeCl₂ coming from a pickling bath. This process forces ferrous chloride to be concentrated and requires chlorination in two stages.

Ce brevet montre dans l'exemple 3 l'impossibilité en utilisant un seul réacteur de chlorer complètement le chlorure ferreux avec la quantité stoechiométrique de chlore, ou l'obligation d'utiliser un excédent de chlore pour chlorer tout le chlorure ferreux.This patent shows in example 3 the impossibility using a single reactor to completely chlorinate ferrous chloride with the stoichiometric amount of chlorine, or the obligation to use an excess of chlorine to chlorinate all ferrous chloride.

Dans la réalisation de cette invention selon le schéma expliqué dans l'exemple 4 on montre la chloration du FeCl₂ en FeCl₃ mais en deux réacteurs qui sont alimentés par un mélange FeCl₂/FeCl₃.In carrying out this invention according to the scheme explained in Example 4, the chlorination of FeCl₂ to FeCl₃ is shown, but in two reactors which are fed with a FeCl₂ / FeCl₃ mixture.

On a maintenant trouvé un procédé qui permet de convertir tout le chlorure ferreux avec la quantité stoechiométrique de chlore en un seul réacteur.We have now found a process which makes it possible to convert all the ferrous chloride with the stoichiometric quantity of chlorine in a single reactor.

La présente invention concerne un procédé de synthèse du chlorure ferrique à partir du chlorure ferreux et en présence de chlorure ferrique caractérisé en ce qu'il consiste à introduire la majeure partie du chlorure ferreux au sommet d'un réacteur essentiellement vertical, à introduire la majeure partie du chlore au pied du réacteur, à introduire un courant latéral de chlorure ferrique dans le réacteur et à recueillir en pied dudit réacteur une solution contenant essentiellement du chlorure ferrique.The present invention relates to a process for the synthesis of ferric chloride from ferrous chloride and in the presence of ferric chloride, characterized in that it consists in introducing the major part of the ferrous chloride at the top of a reactor essentially vertical, to introduce the major part of the chlorine at the bottom of the reactor, to introduce a lateral stream of ferric chloride into the reactor and to collect at the bottom of said reactor a solution containing essentially ferric chloride.

Le réacteur assure la mise en contact du chlore et des chlorure ferreux et ferriques. Le réacteur est essentiellement vertical, c'est-à-dire que c'est une capacité telle que le plus petit cylindre qui contient cette capacité ait une génératrice au moins égale au diamètre de sa section circulaire, cette génératrice étant verticale ou proche de la verticale.The reactor ensures contact between chlorine and ferrous and ferric chloride. The reactor is essentially vertical, that is to say that it is a capacity such that the smallest cylinder which contains this capacity has a generator at least equal to the diameter of its circular section, this generator being vertical or close to the vertical.

On utilise par exemple une colonne du genre colonne à distiller ou colonne d'absorption. On utilise avantageusement une colonne munie de dispositifs de contact gaz/liquide tels que des plateaux ou des garnissages d'anneaux ou de plusieurs de ces dispositifs.For example, a column of the distillation column or absorption column type is used. Advantageously, a column is used fitted with gas / liquid contact devices such as trays or ring linings or more than one of these devices.

La hauteur de cette colonne peut être comprise entre 0,1 et 40 mètres, et de préférence entre 2 et 20 mètres. Le chlorure ferreux se présente sous forme d'une solution aqueuse, de même que le chlorure ferrique. La majeure partie du chlorure ferreux, c'est-à-dire au moins la moitié de la solution est introduite au sommet du réacteur, et le reste de la solution de chlorure ferreux peut être introduit à différentes hauteurs pourvu toutefois que ce soit au-dessus de l'alimentation en chlore qui est la plus proche du pied du réacteur, c'est-à-dire qui géométriquement est la plus basse. Avantageusement on introduit le chlorure ferreux en un seul courant au sommet du réacteur. Le chlorure ferreux est sous forme d'une solution aqueuse contenant essentiellement du chlorure ferreux mais pouvant contenir dejà du chlorure ferrique et/ou de l'acide chlorhydrique.. On peut utiliser du chlore liquide ou gazeux ou un gaz ou un liquide contenant du chlore. La majeure partie du chlore, c'est-à-dire au moins la moitié du courant contenant du chlore est introduite au pied du réacteur et le reste peut être introduit à différentes hauteurs du réacteur.The height of this column can be between 0.1 and 40 meters, and preferably between 2 and 20 meters. Ferrous chloride is in the form of an aqueous solution, as is ferric chloride. Most of the ferrous chloride, i.e. at least half of the solution, is introduced to the top of the reactor, and the remainder of the ferrous chloride solution can be introduced at different heights provided, however, that it is above the chlorine supply which is closest to the bottom of the reactor, that is to say which geometrically is the lowest. Advantageously, the ferrous chloride is introduced in a single stream at the top of the reactor. Ferrous chloride is in the form of an aqueous solution essentially containing ferrous chloride but which may already contain ferric chloride and / or hydrochloric acid. Liquid or gaseous chlorine or a gas or a liquid containing chlorine can be used . Most of the chlorine, that is to say at least half of the chlorine-containing stream, is introduced at the bottom of the reactor and the rest can be introduced at different heights of the reactor.

Avantageusement on introduit le chlore en pied du réacteur.Advantageously, chlorine is introduced at the bottom of the reactor.

On recueille au sommet du réacteur dans la phase gazeuse les inertes contenus dans le chlore et éventuellement le chlore non réagi.The inert materials contained in the chlorine and possibly unreacted chlorine are collected at the top of the reactor in the gas phase.

Le réacteur est alimenté par un courant latéral de chlorure ferrique, ce courant est sous forme d'une solution aqueuse contenant essentiellement du chlorure ferrique. "latéral" veut dire qu' on introduit le chlorure ferrique entre l'alimentation de chlorure ferreux du sommet et l'alimentation de chlore du pied. On ne sortirait pas du cadre de l'invention en utilisant une solution contenant jusqu'à 1% en poids de chlorure ferreux. Ce chlorure ferrique peut aussi contenir un peu d'HCl. Le chlorure ferrique peut être introduit latéralement en plusieurs points. Avantageusement on l'introduit en une fois et de préférence dans le tiers supérieur du réacteur.The reactor is supplied with a side stream of ferric chloride, this stream is in the form of an aqueous solution essentially containing ferric chloride. "lateral" means that we introduce ferric chloride between the supply of ferrous chloride at the top and the supply of chlorine at the foot. It would not be departing from the scope of the invention to use a solution containing up to 1% by weight of ferrous chloride. This ferric chloride can also contain a little HCl. Ferric chloride can be introduced laterally at several points. Advantageously, it is introduced all at once and preferably in the upper third of the reactor.

Avantageusement on utilise une solution de chlorure ferreux et une solution de chlorure ferrique ne contenant pas plus de 1% en poids d'HCl exprimé par rapport au poids des deux solutions de chlorure ferreux et ferrique ce qui permet d'utiliser le chlorure ferrique directement comme agent floculant pour le traitement des eaux.Advantageously, a ferrous chloride solution and a ferric chloride solution containing not more than 1% by weight of HCl expressed relative to the weight of the two ferrous and ferric chloride solutions are used, which allows ferric chloride to be used directly as flocculating agent for water treatment.

Avantageusement le réacteur fonctionne à une température modérée c'est-à-dire telle que cette température ajoutée au temps de séjour ne provoque pas une hydrolyse du FeCl₂.Advantageously, the reactor operates at a moderate temperature, that is to say such that this temperature added to the residence time does not cause hydrolysis of the FeCl₂.

Bien que la réaction entre le chlorure ferreux et le chlore soit totale, avantageusement on respecte un temps de séjour du chlorure ferreux d'au moins 10 secondes dans le réacteur, et de préférence inférieur à 4 heures.Although the reaction between the ferrous chloride and the chlorine is complete, advantageously a residence time of the ferrous chloride is respected of at least 10 seconds in the reactor, and preferably less than 4 hours.

Il n'est pas nécessaire de chlorer tout le FeCl₂, les spécifications du chlorure ferrique peuvent parfois tolérer de 0,1 à 1% en poids de FeCl₂ dans la solution de chlorure ferrique. On ne sortirait pas du cadre de l'invention en utilisant un excès de chlore par rapport à la stoechiométrie.It is not necessary to chlorinate all the FeCl₂, the specifications of ferric chloride can sometimes tolerate 0.1 to 1% by weight of FeCl₂ in the ferric chloride solution. It would not be departing from the scope of the invention to use an excess of chlorine relative to the stoichiometry.

Avantageusement la température du milieu réactionnel est comprise entre 50 et 100°C. La pression peut être quelconque, par commodité on opère entre la pression atmosphérique et 6 bars, et de préférence entre la pression atmosphérique et 1 bar relatif.Advantageously, the temperature of the reaction medium is between 50 and 100 ° C. The pressure can be arbitrary, for convenience, it operates between atmospheric pressure and 6 bars, and preferably between atmospheric pressure and 1 bar relative.

On recueille au pied du réacteur une solution contenant essentiellement du chlorure ferrique. Selon une forme préférée de l'invention cette solution est recyclée au réacteur comme alimentation latérale en chlorure ferrique. En régime stationnaire on soutire avant le recyclage une quantité de chlorure ferrique correspondant en moles à la quantité de chlorure ferreux introduite dans le réacteur. Ce soutirage constitue la production de chlorure ferrique. On peut aussi disposer un échangeur de chaleur sur ce recyclage avant le retour dans le réacteur de manière à extraire les calories dues à la réaction de chloration du chlorure ferreux. On peut aussi évaporer une partie de l'eau de la solution de chlorure ferrique en sortie du réacteur, ou de la solution qu'on soutire, ou de la solution qu'on recycle dans le réacteur ou toute combinaison de ces solutions. Cette évaporation peut être faite par un évaporateur conventionnel ou par exemple par une détente provoquant ainsi une vaporisation de l'eau.A solution containing essentially ferric chloride is collected at the bottom of the reactor. According to a preferred form of the invention, this solution is recycled to the reactor as a lateral supply of ferric chloride. In steady state, a quantity of ferric chloride corresponding to the quantity of ferrous chloride introduced into the reactor is withdrawn before recycling. This racking constitutes the production of ferric chloride. One can also have a heat exchanger on this recycling before returning to the reactor so as to extract the calories due to the chlorination reaction of the chloride. ferrous. It is also possible to evaporate part of the water from the solution of ferric chloride leaving the reactor, or from the solution which is drawn off, or from the solution which is recycled to the reactor or any combination of these solutions. This evaporation can be done by a conventional evaporator or for example by an expansion thus causing a vaporization of the water.

On peut éventuellement réchauffer la solution de chlorure ferrique avant l'évaporation.The ferric chloride solution can optionally be reheated before evaporation.

La figure 1 représente un exemple de mise en oeuvre de l'invention.FIG. 1 represents an example of implementation of the invention.

La colonne (1) qui comprend deux lits de garnissage (7) et (8) est alimentée en (2) en chlorure ferreux, en (3) en chlore et en (4) en chlorure ferrique. On recueille en (6) les inertes contenus dans le courant de chlore (3) et en (5) une solution de chlorure ferrique.The column (1) which comprises two packing beds (7) and (8) is supplied with (2) ferrous chloride, (3) chlorine and (4) ferric chloride. The inert materials contained in the chlorine stream (3) are collected in (6) and in a ferric chloride solution (5).

La figure 2 représente une autre mise en oeuvre de l'invention. (On utilise les mêmes numéro qu'à la figure 1). La solution de chlorure ferrique (5) est détendue en (12). La phase liquide (11) se divise en un courant (9) qui constitue la production de chlorure ferrique et un courant (4) qui est recyclé au réacteur (1). Le pot de détente (12) est relié par (10) à un éjecteur à vapeur. (13) est un échangeur de chaleur.FIG. 2 represents another implementation of the invention. (The same number is used as in Figure 1). The ferric chloride solution (5) is expanded in (12). The liquid phase (11) is divided into a stream (9) which constitutes the production of ferric chloride and a stream (4) which is recycled to the reactor (1). The expansion pot (12) is connected by (10) to a steam ejector. (13) is a heat exchanger.

Les exemples suivants illustrent l'invention sans la limiter.The following examples illustrate the invention without limiting it.

EXEMPLE 1EXAMPLE 1

On utilise un dispositif conforme à la figure 2 dans lequel la colonne (1) est en verre de diamètre intérieur 0,35 m et présente une hauteur de garnissage de 7 m pour la partie (7) et 3 m pour la partie (8).A device is used in accordance with FIG. 2 in which the column (1) is made of glass with an internal diameter of 0.35 m and has a packing height of 7 m for the part (7) and 3 m for the part (8) .

On introduit en (2) une solution de 296 kg/h de FeCl₂ et 704 kg/h d'eau à 80°C et en (3) un débit de 82,7 kg/h de chlore et 5 kg/h d'inertes. On recueille en (6) les 5 kg/h d'inertes et en (5) une solution de chlorure ferrique à 85°C. La colonne (1) opère à une pression de 1,1 bars absolus. On réchauffe le chlorure ferrique de 85 à 94°C par l'échangeur (13), puis on détend à une pression de 0,25 bar absolus. On recycle en (4) une solution contenant 2272 kg/h de FeCl₃ et 3269 kg/h d'eau et on soutire en (10) 379 kg/h de FeCl₃ dilués dans 545 kg/h d'eau.A solution of 296 kg / h of FeCl₂ and 704 kg / h of water at 80 ° C. is introduced in (2) and in (3) a flow rate of 82.7 kg / h of chlorine and 5 kg / h of inert. The 5 kg / h inert material is collected in (6) and in (5) a solution of ferric chloride at 85 ° C. Column (1) operates at a pressure of 1.1 bar absolute. The ferric chloride is heated from 85 to 94 ° C by the exchanger (13), then it is expanded to a pressure of 0.25 bar absolute. A solution containing 2272 kg / h of FeCl₃ and 3269 kg / h of water is recycled in (4) and it is drawn off in (10) 379 kg / h of FeCl₃ diluted in 545 kg / h of water.

EXEMPLE 2 (Comparatif) EXAMPLE 2 (Comparative)

On opère comme dans l'exemple 1 mais en alimentant la colonne (1) avec le chlorure ferreux entre les deux lits (7) et (8), c'est-à-dire à la même hauteur que le recyclage (4). Pour obtenir la même conversion du FeCl₂ en FeCl₃ il a été nécessaire d'augmenter le débit de chlore à 88 kg/h, c'est-à-dire 88 kg/h de chlore et 5,32 kg/h d'inertes. L'excédent de chlore et les inertes sortent en (6).The procedure is as in Example 1 but by feeding the column (1) with ferrous chloride between the two beds (7) and (8), that is to say at the same height as the recycling (4). To obtain the same conversion of FeCl₂ to FeCl₃ it was necessary to increase the chlorine flow rate to 88 kg / h, that is to say 88 kg / h of chlorine and 5.32 kg / h of inert materials. The excess of chlorine and the inert materials come out in (6).

Claims (3)

1. Process for the synthesis of ferric chloride from ferrous chloride and in the presence of ferric chloride, characterised in that it consists
in introducing most, and preferably all, of the ferrous chloride at the top of an essentially vertical reactor, any remainder of ferrous chloride being introduced above the chlorine feed at the bottom,
in introducing most, and preferably all, of the chlorine at the bottom of the reactor,
in introducing a side stream of ferric chloride into the reactor between the ferrous chloride feed at the top and the chlorine feed at the bottom
and in collecting at the bottom of the said reactor a solution containing essentially ferric chloride.
2. Process according to Claim 1, characterised in that the reactor is a column containing devices for gas/liquid contact.
3. Process according to either of Claims 1 or 2, characterised in that the side stream of ferric chloride is introduced into the upper third of the reactor.
EP19890401038 1988-04-29 1989-04-14 Process for the synthesis of iron (iii) chloride Expired - Lifetime EP0340070B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT89401038T ATE65478T1 (en) 1988-04-29 1989-04-14 PROCESS FOR THE PRODUCTION OF FERROUS CHLORIDE.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8805799 1988-04-29
FR8805799A FR2630724B1 (en) 1988-04-29 1988-04-29 FERRIQUE CHLORIDE SYNTHESIS PROCESS

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EP0340070A1 EP0340070A1 (en) 1989-11-02
EP0340070B1 true EP0340070B1 (en) 1991-07-24

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EP19890401038 Expired - Lifetime EP0340070B1 (en) 1988-04-29 1989-04-14 Process for the synthesis of iron (iii) chloride

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US (1) US5118489A (en)
EP (1) EP0340070B1 (en)
JP (1) JP2574729B2 (en)
KR (1) KR920008521B1 (en)
CN (1) CN1019000B (en)
AT (1) ATE65478T1 (en)
AU (1) AU611016B2 (en)
CA (1) CA1335691C (en)
DE (1) DE68900151D1 (en)
DK (1) DK172421B1 (en)
ES (1) ES2023285B3 (en)
FI (1) FI96413C (en)
FR (1) FR2630724B1 (en)
GR (1) GR3002382T3 (en)
IE (1) IE61630B1 (en)
NO (1) NO178021C (en)
PT (1) PT90426B (en)
ZA (1) ZA893092B (en)

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2630723B1 (en) * 1988-04-29 1990-07-13 Atochem PROCESS FOR THE PREPARATION OF FERRIC CHLORIDE FROM DILUTED HYDROCHLORIC ACID
FR2630725B1 (en) * 1988-04-29 1990-07-13 Atochem PROCESS FOR THE PREPARATION OF FERRIC CHLORIDE FROM FERROUS CHLORIDE
BE1004975A3 (en) * 1991-06-06 1993-03-09 Solvay Method and installation for making aqueous solutions of ferric chloride.
FR2704849B1 (en) * 1993-05-07 1995-06-23 Atochem Elf Sa Process for the preparation of ferric chloride.
DE69612957T2 (en) * 1996-03-14 2001-09-06 Condoroil Impianti S.R.L., Casale Litta Pickling of stainless steel with continuous catalytic oxidation of the pickling solution
CA2397820A1 (en) * 2000-01-18 2001-07-26 Mars Technologies, Inc. Ferrous chloride conversion
US20030211031A1 (en) * 2001-01-18 2003-11-13 Temyanko Valery L. Ferrous chloride conversion
US8071067B2 (en) * 2009-05-26 2011-12-06 Kemira Water Solutions, Inc. Processes for making stable ferric chloride solutions
WO2011147426A1 (en) * 2010-05-24 2011-12-01 Mohammed Mohammed Mohammed Saad A process of production of concentrated ferric chloride solution from the waste hydrochloric acid pickle liquor
CN104609477B (en) * 2015-02-03 2016-05-11 上海拱极化学有限公司 A kind of preparation method of high-purity anhydrous ferric trichloride
WO2017199870A1 (en) * 2016-05-16 2017-11-23 東ソー・ファインケム株式会社 Aluminum-oxide-forming composition and method of producing same, and polyolefin-based polymer nanocomposite containing zinc oxide particles or aluminum oxide particles and method of producing same

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US1054400A (en) * 1910-06-08 1913-02-25 Dow Chemical Co Method of making ferric chlorid.
US2096855A (en) * 1934-07-27 1937-10-26 Innis Speiden & Co Manufacture of ferric chloride
BE641141A (en) * 1963-12-11 1964-06-11
JPS5224518B2 (en) * 1973-03-05 1977-07-01
US3873678A (en) * 1973-08-02 1975-03-25 Nl Industries Inc Method for making ferric chloride
US3926614A (en) * 1974-04-19 1975-12-16 Du Pont Ilmenite beneficiation with fecl' 3 'glaeser; hans hellmut
JPS5193552A (en) * 1975-02-14 1976-08-17 HAIGASUOYOBI HAISUINOSHORIHO
GB1495035A (en) * 1975-08-13 1977-12-14 Ucb Sa Continuous process for the preparation of an aqueous solution of ferric chloride
FR2410629A1 (en) * 1977-11-30 1979-06-29 Azanza Berrueta Esteban Ferric chloride prepn. - from waste ferrous chloride soln. e.g. from etching processes, by chlorination and concn.
FR2630723B1 (en) * 1988-04-29 1990-07-13 Atochem PROCESS FOR THE PREPARATION OF FERRIC CHLORIDE FROM DILUTED HYDROCHLORIC ACID
FR2630725B1 (en) * 1988-04-29 1990-07-13 Atochem PROCESS FOR THE PREPARATION OF FERRIC CHLORIDE FROM FERROUS CHLORIDE
JP3607958B2 (en) * 1995-10-13 2005-01-05 株式会社ニコン Retro focus lens

Also Published As

Publication number Publication date
GR3002382T3 (en) 1992-12-30
DK208189D0 (en) 1989-04-28
JP2574729B2 (en) 1997-01-22
EP0340070A1 (en) 1989-11-02
ZA893092B (en) 1990-01-31
JPH01317129A (en) 1989-12-21
DK208189A (en) 1989-10-30
FI892060A0 (en) 1989-04-28
US5118489A (en) 1992-06-02
NO178021C (en) 1996-01-10
DE68900151D1 (en) 1991-08-29
FR2630724A1 (en) 1989-11-03
FR2630724B1 (en) 1990-07-13
NO178021B (en) 1995-10-02
CN1037881A (en) 1989-12-13
KR890015963A (en) 1989-11-27
KR920008521B1 (en) 1992-10-01
FI96413B (en) 1996-03-15
FI96413C (en) 1996-06-25
NO891785L (en) 1989-10-30
PT90426A (en) 1989-11-10
IE61630B1 (en) 1994-11-16
ATE65478T1 (en) 1991-08-15
DK172421B1 (en) 1998-06-08
CA1335691C (en) 1995-05-30
PT90426B (en) 1994-09-30
AU3372389A (en) 1989-11-02
CN1019000B (en) 1992-11-11
IE891405L (en) 1989-10-29
NO891785D0 (en) 1989-04-28
ES2023285B3 (en) 1992-01-01
AU611016B2 (en) 1991-05-30
FI892060A (en) 1989-10-30

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